Chapter 3 - Molecular Symmetry

Symmetry helps us understand molecular structure, some chemical

properties, and characteristics of physical properties (spectroscopy) –
used with group theory to predict vibrational spectra for the
identification of molecular shape, and as a tool for understanding
electronic structure and bonding.

Symmetrical: implies the species possesses a

number of indistinguishable configurations.

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Group Theory: mathematical treatment of symmetry.

symmetry operation – an operation performed on an object

which leaves it in a configuration that is indistinguishable
from, and superimposable on, the original configuration.

symmetry elements – the points, lines, or planes to which a

symmetry operation is carried out.

Element Operation Symbol

Identity Identity E
Symmetry plane Reflection in the plane σ
Inversion center Inversion of a point x,y,z to -x,-y,-z i
Proper axis Rotation by (360/n)° Cn
1. Rotation by (360/n)°
Improper axis Sn
2. Reflection in plane perpendicular to rotation axis

Proper axes of rotation (Cn)

Rotation with respect to a line (axis of rotation).
•Cn is a rotation of (360/n)°.
•C2 = 180° rotation, C3 = 120° rotation, C4 = 90° rotation, C5 = 72° rotation, C6 = 60° rotation…
•Each rotation brings you to an indistinguishable state from the original.

However, rotation by 90° about

the same axis does not give back
the identical molecule. XeF4 is square planar.
Therefore H2O does NOT possess
It has four different C2 axes.
a C4 symmetry axis.
A C4 axis out of the page is
called the principle axis
because it has the largest n.
By convention, the principle
axis is in the z-direction

2
BF3

3
 Reflection through a planes of symmetry (mirror plane)

If reflection of all parts of a molecule through a plane

produced an indistinguishable configuration, the symmetry
element is called a mirror plane or plane of symmetry.
σv(vertical): plane colinear with principal axis

Reflection through a planes of symmetry (mirror plane)

σd(dihedral) Vertical, parallel to principal axis, σ parallel to Cn

and bisecting two C2' axes

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 Reflection through a planes of symmetry (mirror plane)

σh(horizontal): plane perpendicular to principal axis

Inversion, Center of Inversion (i)

A center of symmetry: A point at the center of the molecule. (x,y,z)  (-x,-y,-z).

It is not necessary to have an atom in the center (e.g. benzene).

Tetrahedrons, triangles, and pentagons don't have a center of inversion symmetry.

C2H6 Ru(CO)6 C4H4Cl2F2

5
 Rotation-reflection, Improper rotation(Sn)
This is a compound operation combining a rotation 360/n (Cn) with a
reflection through a plane perpendicular to the Cn axis σh.(Cn followed by σh)

σCn=Sn

An improper rotation (or rotation–reflection), Sn, involves rotation about 360/n

followed by reflection through a plane that is perpendicular to the rotation axis.

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 Identity (E)

Simplest symmetry operation. All molecules have this element. If the

molecule does have no other elements, it is asymmetric.

The identity operation amounts to doing nothing to a molecule and

so leaves any molecule completely unchanged.

CHFClBr SOFCl

Successive Operations

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 Symmetry Point Groups

•Symmetry of a molecule located on symmetry axes, cut by

planes of symmetry, or centered at an inversion center is
known as point symmetry.

•Collections of symmetry operations constitute mathematical

groups.

•Each symmetry point group has a particular designation.

Cn, Cnh, Cnv Dn, Dnh, Dnd S2n Cv , Dh

Ih, I Td , Th ,T Oh,O C1,Ci, Cs

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 HCl F2

Cv Dh
Linear molecular species can be classified according to whether they
possess a centre of symmetry (inversion centre) or not.

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 Tetrahedral Geometry

P4 B4Cl4

Octahedral Geometry Icosahedral Geometry

[W(CO)6] [B12H12]2

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 Identify the symmetry elements that are present in benzene.

Scheme for assigning point groups of molecules and molecular ions

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 Cn Point Groups

Cnn  E

PBrClF C1 H2O2 C2

As(C6H5)3

C3 M(NH2CH2CO2)4 C4

Cnh Point Groups

The direction of the Cn axis is take as vertical, so a symmetry
plane perpendicular to it is a horizontal plane, h.

HOCl NH2F
BBrClF

The point group is called Cs (C1h)

N2F2 B(OH)3

C2h C3h

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 Cnv Point Groups
If a mirror plane contains the rotational axis, the group is called a Cnv group.

H2O SF4

C2v C2v

NF3 CHCl3 SF5Cl

C3v C3v C4v

Dn and Dnh Point Groups

Adding a C2 axis perpendicular to a Cn axis generates one of the dihedral groups.

There must be n
C2 axes
perpendicular to
Cn
Angle between rings not 0° or 90°
D2 D3

Adding a h to a Dn group generates a Dnh group.

C2H4 [PtCl4]2-
D2h D4h

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 BF3

D3h

Dnd Point Groups

Adding a vertical mirror plane to a Dn group in such a fashion

to bisect adjacent C2 axes generates a Dnd group.

D2d

Ferrocene
Fe(C5H5)2
D5d

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 Sn groups

For odd n, (Sn)n = h

For even n, (Sn)n = E

The Sn for odd n is the same as the Cnh.

1,3,5,7-tetrafluorocyclooctatetraene Absence of mirror planes distinguish Sn

groups from Dnd groups.

Linear Groups

H-Cl O=O

Cv Dh

Has a h

High Symmetry Molecules

CCl4 SF6 C60

Td Oh Ih

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The letter ‘A’. tetrachloroplatinate(II)

GeH3F HOCl
SF6
H
O

SeH3F
B(OH)3
B
H

O O

AsBr5 (trigonal bipyramid) H

BH3
B

trans rotamer of Si2H6 H H

Ni(en)3
Crown-shaped S8

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 Characteristic symmetry elements of
some important classes of point groups.

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 Character Tables

•Character tables contain, in a highly symbolic form, information

about how something of interest (an bond, an orbital, etc.) is affected
by the operations of a given point group.
•Each point group has a unique character table, which is organized
into a matrix.
•Column headings are the symmetry operations, which are grouped
into classes.
•Horizontal rows are called irreducible representations of the point
group.
•The main body consists of characters (numbers), and a section on
the right side of the table provides information about vectors and
atomic orbitals.
C2v E C2 σv(xz) σv’(yz)
A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 –1 Rz xy
B1 1 -1 1 –1 x, Ry xz
B2 1 –1 –1 1 y, Rx yz

C3v E 2C3 3σv

A1 1 1 1 z x2 + y2, z2
A2 1 1 -1 Rz
E 2 -1 0 (x,y), (Rx, Ry) (x2-y2, xy)(xz, yz)

•Symmetry elements possessed by the point group are in the top row
•Left hand column gives a list of symmetry labels
•Gives information about degeneracies (A and B indicate non-
degenerate, E refers to doubly degenerate, T means triply
degenerate)
•Main part of table contains characters (numbers) to label the
symmetry properties (of MO’s or modes of molecular vibrations)

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To obtain from this total set the representations for vibration only, it
is necessary to subtract the representations for the other two forms
of motion: rotation and translation. z

z
O y
z x z

y H y H y

x x
x
Cartesian displacement vectors for a water molecule
Translational Modes Rotational Modes
A mode in which A mode in which
all atoms are atoms move to
moving in the rotate (change
same direction, the orientation
equivalent to of) the molecule.
moving the There are 3
molecule. rotational modes
for nonlinear
molecules, and 2
rotational modes
for linear
molecules.

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 Selection Rules: Infrared and Raman Spectroscopy
Infrared energy is absorbed for certain changes in vibrational
energy levels of a molecule.
-for a vibration to be infrared active, there must be a change in
the molecular dipole moment vector associated with the vibration.

For a vibration mode to be Raman active, there must be a change

in the net polarizability tensor
-polarizability is the ease in which the electron cloud associated
with the molecule is distorted

For centrosymmetric molecules, the rule of mutual exclusion

states that vibrations that are IR active are Raman inactive, and
vice versa

The transition from the vibrational ground state to the first

excited state is the fundamental transition.

The two bending modes require the same amount

of energy and are therefore degenerate.

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 C2v E C2 σv(xz) σv’(yz)
A1 1 1 1 1 z x2, y2, z2
z
A2 1 1 -1 –1 Rz xy
y B1 1 -1 1 –1 x, Ry xz
B2 1 –1 –1 1 y, Rx yz

If the symmetry label (e.g. A1, B1, E) of a normal mode of

vibration is associated with x, y, or z in the character table, then
the mode is IR active.
If the symmetry label (e.g. A1, B1, E) of a normal mode of
vibration is associated with a product term (x2, xy) in the
character table, then the mode is Raman active.

C2v E C2 σv(xz) σv’(yz)

A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 –1 Rz xy
B1 1 -1 1 –1 x, Ry xz
B2 1 –1 –1 1 y, Rx yz

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 D 3h E 2C 3 3C 2 hh 2S 3 3
3 vv
A 1 1 1 1 1 1 1 x 2 + y 2, z 2
A2 1 1 -1 1 1 -1 Rz
E 2 -1 0 2 -1 0 (x , y ) (x 2 – y 2, 2xy )
A 1 1 1 1 -1 -1 -1
A2 1 1 -1 -1 -1 1 z
E  2 -1 0 -2 1 0 (R x , R y ) (xy , yz )

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 The vibrational modes of CH4 (Td), only two of which are IR active.

CCl4 http://fy.chalmers.se/OLDUSERS/brodin/MolecularMotions/CCl4spectra.html

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vibrational modes of [PtCl4]2 (D4h)

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Point groups of octahedral metal carbonyl complexes

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 Enantiomers

A pair of enantiomers consists of two molecular species which are

mirror images of each other and are nonsuperposable.

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 Group Theory
Supplemental Material

Character Table Development

Up to this point, we have C2 v

(xz) z
considered symmetry operations
only insofar as they affect atoms
occupying points in molecules. v’
(yz) y
Consider a water molecule (H2O).
x
Coordinates are assigned according to the convention that the highest
fold axis of rotation is aligned with the z-axis, and the x axis is
perpendicular to the plane of the molecule.
Let the translation of the molecule in the +y direction be represented
by unit vectors on the atoms, and consider how they change when
undergoing the C2v symmetry operations.
z O O O O

H H H H H H H H
E C2 v (xz) v (yz)
y
O O O O
x
H H H H H H H H
B2 = +1 -1 -1 +1

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 The set of four labels (+1, -1, -1, +1) generated in the analysis
constitutes one irreducible representation within the C2v point
group. It is irreducible in the sense that it cannot be decomposed
into a simpler or more fundamental form.
•Not only does it describe the effects on the y translation but also
on other ‘y-vector functions’ such as a py orbital.
•Therefore, y is understood to serve as a basis function for this
irreducible representation within the C2v point group.
Effect of a symmetry rotation about the z-axis.

z O O O O

H H H H H H H H
E C2 v (xz) v (yz)
y

x
O O O O

H H H H H H H H
A2 = +1 +1 -1 -1

Translation of the molecule in the +x direction

z O O O O

H H H H H H H H
E C2 v (xz) v (yz)
y
O O O O
x
H H H H H H H H
B1 =
+1 -1 +1 -1

Translation of the molecule in the +z direction

z O O O O

H H H H H H H H
E C2 v (xz) v (yz)
y

x O O O O
A1 = H H H H H H H H
+1 +1 +1 +1

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 C2v E C2 σv(xz) σv(yz)
A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 –1 Rz xy
B1 1 -1 1 –1 x, Ry xz
B2 1 –1 –1 1 y, Rx yz

The resulting character table for C2v is shown above.

The column heading are classes of symmetry operations for the
group, and each row depicts one irreducible representation.
The +1 and -1 numbers, which correspond to symmetric and
antisymmetric behavior, are called characters.
Columns on the right are some of the basis functions which have
the symmetry properties of a given irreducible representation.
Rx, Ry, Rz stand for rotations about the specified axes.
Symbols in the column on the far left are Mulliken Labels.

Reducible Representations

When applying the methods of group theory to problems

related to molecular structure or dynamics, the procedure
that is followed usually involves deriving a reducible
representation for the phenomenon of interest, such as a
molecular vibration, and then decomposing it into its
irreducible components.
A reducible representation will always be a sum of
irreducible representations.
In some cases (simple molecules with few bonds) we can
perform the decomposition by inspection, for the more
general case (complicated molecule with many bonds),
we can use the reduction formula.

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 Reducible Representations
The reduction can be achieved using the reduction formula. It is a
mathematical way of reducing that will always work when the answer
cannot be spotted by eye. It is particularly useful when there are
large numbers of bonds involved.

The vibrational modes of the molecule are reduced to produce a

reducible representation into the irreducible representations. This
method uses the following formula reduction formula:

1
N 
h x
 rx  ix n x

N is the number of times a symmetry species occurs in the reducible

representation,
h is the ‘order of the group’: simply the total number of symmetry operations in
the group.
The summation is over all of the symmetry operations. For each symmetry
operation, three numbers are multiplied together. These are:
Χr character of the reducible representation for the operations of the class
Χi character of the irreducible representation for the operations of the class
n is the number of symmetry operations in the class

The characters of the reducible representation can be determined

by considering the combined effect of each symmetry operation on
the atomic vectors. z z
Atomic contributions, by symmetry operations, E
to the reducible representation for the 3N
degrees of freedom for a molecule. y y
Operation Contribution
x x
per atom*
E 3 z z

C2 -1
(xz)
C3 0
y y
C4 1
C6 2 x x
 1 z
i -3
i x
S3 -2
y y
S4 -1
S6 0 x z
*Cn = 1 + 2cos(360/n); Sn = -1 + 2cos(360/n)

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 z
Derivation of reducible representation for degrees of freedom in H2O

y Unshifted atoms

x
O O
E 3

Ha Hb Ha Hb

O O
C2
1
Ha Hb Hb Ha
O O
(xz)
1
Ha Hb Hb Ha

O O
(yz)
3
Ha Hb Ha Hb

Obtain the reducible representation (for H2O)

by multiplying the number of unshifted atoms
times the contribution per atom.

E C2 v(xz) v(yz)
Unshifted Atoms 3 1 1 3
Contribution per atom 3 -1 1 1
tot 9 -1 1 3

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 Reducible Representations
The reduction can be achieved using the reduction formula. It is a
mathematical way of reducing that will always work when the answer
cannot be spotted by inspection. It is particularly useful when there
are large numbers of atoms and bonds involved.

The vibrational modes of the molecule are reduced to produce a

reducible representation into the irreducible representations. This
method uses the following formula reduction formula:

1
N 
h x
 rx  ix n x
N is the number of times a symmetry species occurs in the reducible
representation,
h is the ‘order of the group’: simply the total number of symmetry operations in
the group.
The summation is over all of the symmetry operations. For each symmetry
operation, three numbers are multiplied together. These are:
Χr is the character for a particular class of operation in the reducible
representation
Χi is the character of the irreducible representation.
n is the number of symmetry operations in the class

Tabulate our known information.

Reducible Representation (for H2O)
1) E C2 v(xz) v(yz)
r 9 -1 1 3
Character Table
2)
C2v E C2 σv(xz) σv(yz) h=4
A1 1 1 1 1 z x2, y2, z2
1
A2
B1
1
1
1
-1
–1
1
–1 Rz
–1 x, Ry
xy
xz
N 
h x
 rx  ix n x
B2 1 –1 –1 1 y, Rx yz
irrep
A1: (1/h)[(rE)(iE)(nE) + (rC2)(iC2)(nC2) + (r v(xz))(iv(xz))(nv(xz))
+ (r v(yz))(iv(yz))(nv(yz))]
A : (1/4)[(9)( E)(nE) + (-1)( C2)(nC2) + (1)( v(xz))(nv(xz)) +
1 i i i
(3)(iv(yz))(nv(yz))]

A1: (1/4)[(9)(1)(nE) + (-1)(1)(nC2) + (1)(1)(nv(xz)) + (3)(1)(nv(yz))]

A1: (1/4)[(9)(1)(1) + (-1)(1)(1) + (1)(1)(1) + (3)(1)(1)] = 3

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 Calculate irreducible representation A2

A2: (1/h)[(rE)(iE)(nE) + (rC2)(iC2)(nC2) + (r v(xz))(iv(xz))(nv(xz))

+ ( v(yz))( v(yz))(nv(yz))
r i
A2: (1/4)[(9)(1)(1) + (-1)(1)(1) + (1)(-1)(1) + (3)(-1)(1) = 1

Calculate irreducible representation B1

B1: (1/4)[(9)(1)(1) + (-1)(-1)(1) + (1)(1)(1) + (3)(-1)(1) = 2

Calculate irreducible representation B2

B2: (1/4)[(9)(1)(1) + (-1)(-1)(1) + (1)(-1)(1) + (3)(1)(1) = 3

The reducible representation…

E C2 v(xz) v(yz)
r 9 -1 1 3

…is resolved into three A1, one A2, two B1, and three B2 species.

C2v E C2 σv(xz) σv(yz)

A1 1 1 1 1 z x2, y2, z2
A2 1 1 –1 –1 Rz xy
B1 1 -1 1 –1 x, Ry xz
B2 1 –1 –1 1 y, Rx yz

tot = 3A1 + A2 + 2B1 + 3B2

-[trans = A1 + B1 + B2]
-[rot = A2 + B1 + B2]
vib = 2A1 + B2

Notice this is the same result we

obtained by analyzing the symmetries
of the vibrational modes.
-each mode is IR active

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Consider only the OH stretches in H2O
-consider the number of unchanged O-H bonds under the symmetry
operations of the point group

C2v E C2 σv(xz) σv(yz) Reducible

Unchanged OH bonds 2 0 0 2 Representation

C2v E C2 σv(xz) σv(yz)

A1 1 1 1 1 z x2, y2, z2
Character A2 1 1 –1 –1 Rz xy
Table
B1 1 -1 1 –1 x, Ry xz
B2 1 –1 –1 1 y, Rx yz
By inspection, the reducible representation is composed of the A1
and B2 representation.
E C2 σv(xz) σv(yz)
A1 1 1 1 1
B2 1 -1 -1 1
Sum of rows 2 0 0 2

General Method: Determine OH stretching in H2O using

reducible representations and reduction formula
C2v E C2 σv(xz) σv(yz)
Coefficient 1 1 1 1
Order of group 4
Unchanged bonds (OH) 2 0 0 2

C2v E C2 σv(xz) σv(yz)

A1 1 1 1 1 z x2, y2, z2
A2 1 1 –1 –1 Rz xy
B1 1 -1 1 –1 x, Ry xz
B2 1 –1 –1 1 y, Rx yz

Using reducible representations and the reduction

formula, one obtains A1 + B2 modes.

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 Derive tot for BCl3 given the character table for D3h
Derive the number of vibrational modes and assign modes for BCl3.

E 2C3 3C2 h 2S3 3v

Unshifted atoms 4 1 2 4 1 2
Contribution per atom 3 0 -1 1 -2 1
tot 12 0 -2 4 -2 2

D 3h E 2C 3 3C 2 hh 2S 3 3
3 vv
A 1 1 1 1 1 1 1 x 2 + y 2, z 2
A2 1 1 -1 1 1 -1 Rz
E 2 -1 0 2 -1 0 (x , y ) (x 2 – y 2, 2xy )
A 1 1 1 1 -1 -1 -1
A2 1 1 -1 -1 -1 1 z
E  2 -1 0 -2 1 0 (R x , R y ) (xy , yz )

Results of using the reduction formula.

x x x
Χr *Χi *n 1/h Sum Total
A 1 12 0 -6 4 -4 6 0.083333 12 1
A 2 12 0 6 4 -4 -6 0.083333 12 1
E 24 0 0 8 4 0 0.083333 36 3
A 1 12 0 -6 -4 4 -6 0.083333 0 0
A 2 12 0 6 -4 4 6 0.083333 24 2
E  24 0 0 -8 -4 0 0.083333 12 1
Therefore, we have determined
tot = A1 + A 2 +3 E+2 A 2 + E 
but, subtract off the translational representations.

-[trans = E + A 2 ] Each E’

representation
and subtract off the rotational representations. describes two
-[rot = A 2 + E  ] vibrational
modes of equal
vib = A1 +2 E + A 2 ] energy.

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 Symmetrical Out-of-plane Unsymmetrical In-plane
stretching. bending mode. stretching. bending mode.

Raman active. IR active. Raman and IR active.

We can use isotopic substitution to interpret spectra, since the

characteristic frequency of the mode will depend on the masses of
the atoms moving in that mode.

Review: What do I do when I need to…?

Assign symmetry labels to vibrational modes?

•If the vibrational mode is known and illustrated, sketch the resulting
vibrational mode before and after each symmetry operation of the
point group. Using the character table, assign the symmetry label and
identify if the mode is IR and/or Raman active.
Determine the symmetries of all vibrational modes and if the modes
are IR and/or Raman active?
•Determine how many atoms are left unchanged by each symmetry
operation. Find the reducible representation and reduce into the
irreps. Subtract translational and rotational modes… Identify which
modes are IR and/or Raman active.…
Determine the symmetries of only the stretching modes and if the
modes are IR and/or Raman active?
•Determine how many bonds are left unchanged by each symmetry
operation. Find the reducible representation and reduce into the
irreps. Identify which are IR and/or Raman active.…
Develop a character table?
•Determine the effect of each symmetry operation on the x, y, z
translation and the rotation Rx, Ry, and Rz. The resulting set of
characters correspond to an irrep in the character table.

36
Determine the number of and assign the vibrational modes of the following:
How many peaks in the (1) IR spectra and (2) Raman spectra

1. NH3
2. CH4
3. [PtCl4]2-
4. SF6
5. SF5Cl

Determine the symmetries and number of vibrational modes, and number

IR and Raman peaks for a) CO stretching modes b) all vibrational modes:
1. Mn(CO)6
2. Mn(CO)5Cl
3. trans-Mn(CO)4Cl2
4. cis-Mn(CO)4Cl2
5. fac-Mn(CO)3Cl3
6. mer-Mn(CO)3Cl3

37